Heterocyclic fluoroalkenyl thioethers (II)

ABSTRACT

The present invention relates to novel heterocyclic fluoroalkenyl thioethers of the formula (I) 
                 
 
in which
     X represents hydrogen, halogen or alkyl,   m represents integers from 3 to 10,   n represents 0, 1 or 2,   Het represents the groups 
                 
 
where
       R 1  represents hydrogen; mercapto; optionally halogen-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl or alkenyl; optionally substituted aryl; or optionally substituted heterocyclyl,   Y represents oxygen or sulphur, and   R 2  represents hydrogen, alkyl or optionally substituted aryl,
 
and to processes for their preparation and to their use as pesticides.

The present invention relates to novel heterocyclic fluoroalkenylthioethers, to processes for their preparation and to their use aspesticides.

It is known that certain heterocyclic fluoroalkenyl thioethers haveinsecticidal, acaricidal and/or nematicidal properties (cf., forexample, U.S. Pat. No. 3,914,251, U.S. Pat. No. 5,952,359, WO 99/52874,WO 99/52882 or JP 11140063). However, in particular at low applicationrates and concentrations of active compound, the efficacy and/oractivity spectrum of these compounds is not always entirelysatisfactory.

This invention provides novel heterocyclic fluoroalkenyl thioethers ofthe formula (I)

in which

-   X represents hydrogen, halogen or alkyl,-   m represents integers from 3 to 10,-   n represents 0, 1 or 2,-   Het represents the groupings    -   where    -   R¹ represents hydrogen, mercapto, represents in each case        optionally halogen-substituted alkyl, alkoxy, alkylthio,        alkylsulphinyl, alkylsulphonyl, alkenyl, alkenylthio,        alkenylsulphinyl or alkenylsulphonyl, represents optionally        substituted aryl or represents optionally substituted        heterocyclyl,    -   Y represents oxygen or sulphur and    -   R² represents hydrogen, alkyl or optionally substituted aryl.

Furthermore, it has been found that the heterocyclic fluoroalkenylthioethers of the formula (I) are obtained when

-   a) mercapto derivatives of the formula (II)    Het-SH  (II)    -   in which    -   Het is as defined above    -   are reacted with fluoroalkenyl halides of the formula (III)    -   in which    -   X and m are each as defined above and    -   Hal represents halogen, preferably bromine or chlorine,    -   in the presence of a diluent and if appropriate in the presence        of a basic reaction auxiliary, where it is also possible to use        the compounds of the formula (II) in the form of their salts,        preferably the alkali metal salts, such as, in particular, the        sodium or potassium salts; and, if appropriate,-   b) the resulting heterocyclic fluoroalkenyl thioethers of the    formula (IA) according to the invention    -   in which    -   Het, X and m are each as defined above    -   are oxidized with an oxidizing agent, if appropriate in the        presence of a diluent and if appropriate in the presence of a        catalyst.

Finally, it has been found that the novel heterocyclic fluoroalkenylthioethers of the formula (I) have highly pronounced biologicalproperties and are suitable especially for controlling animal pests, inparticular insects, arachnids and nematodes, encountered in agriculture,in forests, in the protection of stored products and materials and inthe hygiene sector.

The formula (I) provides a general definition of the heterocyclicfluoroalkenyl thioethers according to the invention.

Preferred substituents or ranges of the radicals listed in the formulaementioned above and below are illustrated below:

-   X preferably represents hydrogen, fluorine, chlorine, bromine or    C₁-C₄-alkyl.-   m preferably represents integers from 3 to 8.-   n preferably represents 0 or 2.-   Het preferably represents the groupings.    where    -   R¹ represents hydrogen or mercapto, represents C₁-C₈-alkyl,        C₁-C₈-alkoxy, C₁-C₈-alkylthio, C₁-C₈-alkylsulphinyl,        C₁-C₈-alkylsulphonyl, C₂-C₈-alkenyl, C₂-C₈-alkenylthio,        C₂-C₈-alkenylsulphinyl or C₂-C₈-alkenylsulphonyl, each of which        is optionally mono- or polysubstituted by identical or different        halogens, represents phenyl which is optionally mono- to        pentasubstituted by identical or different substituents from the        group consisting of halogen, nitro, cyano, thiocyanato, and        C₁-C₄-alkyl, C₁-C₄-alkoxy or C₁-C₄-alkylthio, each of which is        optionally mono- or polysubstituted by identical or different        halogens, or represents 5- or 6-membered heterocyclyl having 1        to 3 N, O or S heteroatoms, which is optionally mono- to        pentasubstituted by identical or different substituents from the        group consisting of halogen, nitro, cyano, thiocyanato, and        C₁-C₄-alkyl, C₁-C₄-alkoxy or C₁-C₄-alkylthio, each of which is        optionally mono- or polysubstituted by identical or different        halogens.    -   Y preferably represents oxygen or sulphur, and    -   R² represents hydrogen or C₁-C₄-alkyl.-   X particularly preferably represents hydrogen or fluorine.-   m particularly preferably represents integers from 3 to 6.-   n particularly preferably represents 0.-   Het particularly preferably represents the groupings    where    -   R¹ represents hydrogen or mercapto, represents C₁-C₆-alkyl,        C₁-C₆-alkoxy, C₁-C₆-alkylthio, C₁-C₆-alkylsulphinyl,        C₁-C₆-alkylsulphonyl, C₂-C₆-alkenyl, C₂-C₆-alkenylthio,        C₂-C₆-alkenylsulphinyl or C₂-C₆-alkenylsulphonyl, each of which        is optionally mono- to pentasubstituted by identical or        different substituents from the group consisting of fluorine and        chlorine, represents phenyl which is optionally mono- to        trisubstituted by identical or different substituents from the        group consisting of fluorine, chlorine, bromine, nitro, cyano,        thiocyanato, and C₁-C₄-alkyl, C₁-C₄-alkoxy or C₁-C₄-alkylthio,        each of which is optionally mono- to pentasubstituted by        identical or different substitutents from the group consisting        of fluorine and chlorine, or represents furyl, thienyl,        pyrazolyl, pyridinyl or pyrimidinyl, each of which is optionally        mono- to trisubstituted by identical or different substituents        from the group consisting of fluorine, chlorine, bromine, nitro,        cyano, thiocyanato, and C₁-C₄-alkyl, C₁-C₄-alkoxy or        C₁-C₄-alkylthio, each of which is optionally mono- to        pentasubstituted by identical or different substituents from the        group consisting of fluorine and chlorine.    -   Y represents oxygen or sulphur, and    -   R² represents hydrogen or C₁-C₄-alkyl.-   m very particularly preferably represents 4.-   Het very particularly preferably represents the groupings    where    -   R¹ represents hydrogen or mercapto, represents methyl, ethyl, n-        or i-propyl, n-, i-, s-, or t-butyl, n-, i- or neo-pentyl,        methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy,        methylthio, ethylthio, n- or i-propylthio, methylsulphinyl,        ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl,        ethylsulphonyl, n- or i-propylsulphonyl, each of which is        optionally mono- to pentasubstituted by identical or different        substituents from the group consisting of fluorine and chlorine,        represents ethenyl, propenyl, butenyl, pentenyl or hexenyl,        represents ethenylthio, propenylthio, butenylthio, pentenylthio        or hexenylthio, represents ethylsulphinyl, propenylsulphinyl,        butenylsulphinyl, pentenylsulphinyl or hexenylsulphinyl,        represents ethenylsulphonyl, propenylsulphonyl,        butenylsulphonyl, pentenylsulphonyl or hexenylsulphonyl,        represents phenyl which is optionally mono- or disubstituted by        identical or different substituents from the group consisting of        fluorine, chlorine, nitro, cyano, thiocyanato, and methyl,        ethyl, methoxy, ethoxy, methylthio and ethylthio, each of which        is optionally mono- to pentasubstituted by identical or        different substituents from the group consisting of fluorine and        chlorine, or represents thienyl or pyridinyl, each of which is        optionally mono- or disubstituted by identical or different        substituents from the group consisting of fluorine, chlorine,        nitro, cyano, thiocyanato, and methyl, ethyl, methoxy, ethoxy,        methylthio and ethylthio, each of which is optionally mono- to        pentasubstituted by identical or different substituents from the        group consisting of fluorine and chlorine,    -   Y represents oxygen or sulphur, and    -   R² represents hydrogen, methyl, ethyl, n- or i-propyl.-   Het most preferably represents the grouping    where    -   R¹ and Y have one of the meanings mentioned above as being        preferred, particularly preferred or very particularly preferred        for R¹ and Y.

The abovementioned general or preferred radical definitions orillustrations apply both to the end products and, correspondingly, tothe starting materials and intermediates. These radical definitions canbe combined with one another as desired, i.e. including combinationsbetween the respective preferred ranges.

Preference according to the invention is given to the compounds of theformula (I), which contain a combination of the meanings listed above asbeing preferred (preferable).

Particular preference according to the invention is given to compoundsof the formula (I), which contain a combination of the meanings listedabove as being particularly preferred.

Very particular preference according to the invention is given to thecompounds of the formula (I) which contain a combination of the meaningslisted above as being very particularly preferred.

Most preference according to the invention is given to the compounds ofthe formula (I) which contain a combination of the meanings listed aboveas being most preferred.

In the radical definitions listed above and below, hydrocarbon radicals,such as alkyl, are in each case straight-chain or branched as far asthis is possible—including in combinations with heteroatoms, such asalkoxy.

Using, for example,2-mercapto-5-(4-trifluoromethylphenyl)-1,3,7-oxadiazole and6,6,5-trifluorohex-5-enyl bromide as starting materials, the course ofthe reaction in the process (a) according to the invention can berepresented by the following equation:

Using, for example,2-(6,6,5-trifluorohex-5-enylthio)-5-(4-trifluoromethylphenyl)-1,3,4-oxadiazoleas starting material and H₂O₂ as oxidizing agent and sodium tungstate ascatalyst, the course of the reaction in the process (b) according to theinvention can be represented by the following equation:

The formula (II) provides a general definition of the mercaptoderivatives to be used as starting materials for carrying out process(a) according to the invention.

Most of the mercapto derivatives of the formula (II) are known and/orcan be prepared similarly to known processes (cf., for example,Houben-Weyl, Methoden der organischen Chemie [Methods of OrganicChemistry], volume III/part 3, p. 526ff. and/or volume III/part 4,p.189ff., Georg Thieme Verlag Stuttgart 1994; Helvetia Chim. Acta 55,1178 (1972) or Monatshefte Chemie 113, 793 (1982)).

The formula (III) provides a general definition of the fluoroalkenylhalides furthermore to be used as starting materials in the process (a)according to the invention.

The fluoroalkenyl halides of the formula (III) are known (cf., forexample, J. Chem. Soc. Perkin Trans. 2, 219 (1998); Tetrahedron Lett.37, 5321 (1996); EP 0 334 796 or WO 95/4727), or they are commerciallyavailable.

Suitable diluents for carrying out the process (a) according to theinvention are inert organic solvents. These include, in particular,aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons,such as, for example, benzine, benzene, toluene, xylene, anisole,chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane,dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride;ethers, such as diethyl ether, dioxane, tetrahydrofuran or ethyleneglycol dimethyl ether or ethylene glycol diethyl ether; ketones, such asacetone or butanone; nitriles, such as acetonitrile or propionitrile;amides, such as dimethylformamide, dimethylacetamide,N-methylformanilide, N-methylpyrrolidone or hexamethylphosphorictriamide; esters, such as ethyl acetate; sulphoxides, such as dimethylsulphoxide or sulpholane; but also alcohols, such as methanol, ethanolor isopropanol.

If appropriate, the process (a) according to the invention can becarried out in the presence of a basic reaction auxiliary. Suitablebasic reaction auxiliaries are all customary inorganic or organic bases.These include, for example, alkali metal and alkaline earth metalhydroxides, such as sodium hydroxide, potassium hydroxide or calciumhydroxide, alkali metal carbonates or bicarbonates, such as sodiumcarbonate, potassium carbonate, caesium carbonate or sodium bicarbonate,and also tertiary amines, such as triethylamine, N,N-dimethylaniline,pyridine, N,N-dimethyl-aminopyridine, diazabicyclooctane (DABCO),diazabicyclononene (DBN) or diazabicycloundecene (DBU).

When carrying out the process (a) according to the invention, thereaction temperatures can be varied within a relatively wide range. Ingeneral, the process is carried out at temperatures between 0° C. and+200° C., preferably at temperatures between +20° C. and +140° C.

For carrying out the process (a) according to the invention, in generalfrom 0.3 to 3.0 mol, preferably a slight excess, of fluoroalkenyl halideof the formula (III) and, if appropriate, from 0.5 to 2.0 mol,preferably from 0.5 to 1.0 mol, of reaction auxiliary are employed permole of mercapto derivative of the formula (II). The practice of thereaction and the work-up and isolation of the reaction products arecarried out by generally customary processes.

Suitable oxidizing agents for carrying out the process (b) according tothe invention are all oxidizing agents which are customarily used foroxidizing sulphur. Particularly suitable are hydrogen peroxide, organicand inorganic peracids, such as, for example, peracetic acid,m-chloroperbenzoic acid, p-nitroperbenzoic acid, magnesiumperoxyphthalic acid, potassium peroxymonosulphate or atmospheric oxygen.

Suitable diluents for carrying out the process (b) according to theinvention are likewise inert organic solvents. Preference is given tousing hydrocarbons, such as benzine, benzene, toluene, hexane orpetroleum ether; chlorinated hydrocarbons, such as dichloromethane,1,2-dichloroethane, chloroform, carbon tetrachloride or chlorobenzene;ethers, such as diethyl ether, dioxane or tetrahydrofuran; carboxylicacids, such as formic acid, acetic acid or propionic acid, or dipolaraprotic solvents, such as acetonitrile, acetone, ethyl acetate ordimethylformamide; if appropriate also in aqueous solutions.

If appropriate, the process (b) according to the invention can becarried out in the presence of a suitable catalyst. Suitable catalystsare all metal salt catalysts which are usually employed for such sulphuroxidations. Compounds which may be mentioned in an exemplary manner inthis context are ammonium molybdate and sodium tungstate.

When carrying out the process (b) according to the invention, thereaction temperatures can be varied within a relatively wide range. Ingeneral, the process is carried out at temperatures between −20° C. and+120° C., preferably at temperatures between 0° C. and +100° C.

For carrying out the process (b) according to the invention, in generalfrom 0.8 to 1.2 mol, preferably equimolar amounts, of oxidizing agentare employed per mole of the compound of the formula (Ia) if theoxidation of the sulphur is to be interrupted on the sulphoxide stage.For the oxidation to the sulphone, in general from 1.8 to 3.0 mol,preferably twice the molar amount, of oxidizing agent is employed permole of the compound of the formula (Ia). The practice of the reactionand work-up and isolation of the end products are carried out bycustomary processes.

The active compounds having good plant tolerance and favourablewarm-blood toxicity are suitable for controlling animal pests, inparticular insects, arachnids and nematodes, which are encountered inagriculture, in forestry, in the protection of stored products and ofmaterials, and in the hygiene sector. They may be preferably used ascrop protection agents. They are active against normally sensitive andresistant species and against all or some stages of development. Theabovementioned pests include:

From the order of the Isopoda, for example, Oniscus asellus,Armadillidium vulgare and Porcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of the Chilopoda, for example, Geophilus carpophagus andScutigera spp.

From the order of the Symphyla, for example, Scutigerella immaculata.

From the order of the Thysanura, for example, Lepisma saccharina.

From the order of the Collembola, for example, Onychiurus armatus.

From the order of the Orthoptera, for example, Acheta domesticus,Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp. andSchistocerca gregaria.

From the order of the Blattaria, for example, Blatta orientalis,Periplaneta americana, Leucophaea maderae and Blattella germanica.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Reticulitermes spp.

From the order of the Phthiraptera, for example, Pediculus humanuscorporis, Haematopinus spp., Linognathus spp., Trichodectes spp. andDamalinia spp.

From the order of the Thysanoptera, for example, Hercinothripsfemoralis, Thrips tabaci, Thrips palmi and Frankliniella accidentalis.

From the order of the Heteroptera, for example, Eurygaster spp.,Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus and Triatoma spp.

From the order of the Homoptera, for example, Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosomalanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp.,Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi,Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecaniumcorni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens,Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. and Psyllaspp.

From the order of the Lepidoptera, for example, Pectinophoragossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletisblancardella, Hyponomeuta padella, Plutella xylostella, Malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltiaspp., Earias insulana, Heliothis spp., Mamestra brassicae, Panolisflammea, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pierisspp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleriamellonella, Tineola bisselliella, Tinea pellionella, Hofmannophilapseudospretella, Cacoecia podana, Capua reticulana, Choristoneurafumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana,Cnaphalocerus spp. and Oulema oryzae.

From the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus,Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedoncochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachnavarivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp.,Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogodermaspp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus,Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp.,Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha,Amphimallon solstitialis, Costelytra zealandica and Lissorhoptrusoryzophilus.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis and Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae,Tipula paludosa, Hylemyia spp. and Liriomyza spp.

From the order of the Siphonaptera, for example, Xenopsylla cheopis andCeratophyllus spp.

From the class of the Arachnida, for example, Scorpio maurus,Latrodectus mactans, Acarus siro, Argas spp., Ornithodoros spp.,Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora,Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp.,Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemusspp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.,Hemitarsonemus spp. and Brevipalpus spp.

The plant-parasitic nematodes include, for example, Pratylenchus spp.,Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans,Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp.,Longidorus spp., Xiphinema spp., Trichodorus spp. and Bursaphelenchusspp.

The compounds according to the invention can be used with particularlygood results for controlling plant-damaging nematodes, such as, forexample, againt Meloidogyne incognita larvae, for controllingplant-damaging insects, such as, for example, against the peach aphid(Myzus persicae), the larvae of the mustard beetle (Phaedon cochleariae)and also against the caterpillars of the army worm (Spodopterafrugiperda); and also for controlling plant-damaging spider mites(Tetranychus urticae).

At appropriate application rates, the compounds according to theinvention also have fungicidal properties.

At certain concentrations or application rates, the compounds accordingto the invention may, if appropriate, also be used as herbicides andmicrobicides, for example as fungicides, antimycotics and bactericides.If appropriate, they may also be used as intermediates or precursors forthe synthesis of further active compounds.

All plants and plant parts can be treated in accordance with theinvention. Plants are to be understood as meaning in the present contextall plants and plant populations such as desired and undesired wildplants or crop plants (inclusive of naturally occurring crop plants).Crop plants can be plants which can be obtained by conventional plantbreeding and optimization methods or by biotechnological and recombinantmethods or by combinations of these methods, inclusive of the transgenicplants and inclusive of the plant cultivars protectable or notprotectable by plant breeders' rights. Plant parts are to be understoodto mean all above-ground and underground parts and organs of plants,such as shoot, leaf, flower and root, examples which may be mentionedbeing leaves, needles, stalks, stems, flowers, fruit bodies, fruits,seeds, roots, tubers and rhizomes. The plant parts also includeharvested material, and vegetative and generative propagation material,for example cuttings, tubers, rhizomes, offsets and seeds.

As already mentioned above, it is possible to treat all plants and theirparts according to the invention. In a preferred embodiment, wild plantspecies and plant cultivars, or those obtained by conventionalbiological breeding, such as crossing or protoplast fusion, and partsthereof, are treated. In a further preferred embodiment, transgenicplants and plant cultivars obtained by genetic engineering, ifappropriate in combination with conventional methods (GeneticallyModified Organisms), and parts thereof are treated. The term “parts” or“parts of plants” or “plant parts” has been explained above.

Particularly preferably, plants of the plant cultivars which are in eachcase commercially available or in use are treated according to theinvention. Plant cultivars are to be understood as meaning plants havingnovel properties (“traits”) which can be obtained by conventionalbreeding, by mutagenesis or by recombinant DNA techniques. This can bevarieties, bio- and genotypes.

Depending on the plant species or plant cultivars, their location andgrowth conditions (soils, climate, vegetation period, diet), thetreatment according to the invention may also result in superadditive(“synergistic”) effects. Thus, for example, reduced application ratesand/or a widening of the activity spectrum and/or an increase in theactivity of the substances and compositions to be used according to theinvention, better plant growth, increased tolerance to high or lowtemperatures, increased tolerance to drought or to water or soil saltcontent, increased flowering performance, easier harvesting, acceleratedmaturation, higher harvest yields, better quality and/or a highernutritional value of the harvested products, better storage stabilityand/or processability of the harvested products are possible whichexceed the effects which were actually to be expected.

The transgenic plants or plant cultivars (i.e. those obtained by geneticengineering) which are preferred according to the invention include allplants which, in the genetic modification, received genetic materialwhich imparted particularly advantageous useful traits to these plants.Examples of such properties are better plant growth, increased toleranceto high or low temperatures, increased tolerance to drought or to wateror soil salt content, increased flowering performance, easierharvesting, accelerated maturation, higher harvest yields, betterquality and/or a higher nutritional value of the harvested products,better storage stability and/or processability of the harvestedproducts. Further and particularly emphasized examples of suchproperties are a better defence of the plants against animal andmicrobial pests, such as against insects, mites, phytopathogenic fungi,bacteria and/or viruses, and also increased tolerance of the plants tocertain herbicidally active compounds. Examples of transgenic plantswhich may be mentioned are the important crop plants, such as cereals(wheat, rice), maize, soya beans, potatoes, cotton, oilseed rape andalso fruit plants (with the fruits apples, pears, citrus fruits andgrapevines), and particular emphasis is given to maize, soya beans,potatoes, cotton and oilseed rape. Traits that are emphasized are inparticular increased defence of the plants against insects by toxinsformed in the plants, in particular those formed by the genetic materialfrom Bacillus thuringiensis (for example by the genes CryIA(a),CryIA(b), CryIA(c), CryIIA, CryIIIA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb andCryIF and also combinations thereof) (hereinbelow referred to as “Btplants”). Traits that are also particularly emphasized are the increaseddefence of the plants to fungi, bacteria and viruses by systemicacquired resistance (SAR), systemin, phytoalexius, elicitous andresistance genes and correspondingly expressed proteins and toxins.Traits that are furthermore particularly emphasized are the increasedtolerance of the plants to certain herbicidally active compounds, forexample imidazolinones, sulphonylureas, glyphosate or phosphinotricin(for example the “PAT” gene). The genes which impart the desired traitsin question can also be present in combination with one another in thetransgenic plants. Examples of “Bt plants” which may be mentioned aremaize varieties, cotton varieties, soya bean varieties and potatovarieties which are sold under the trade names YIELD GARD® (for examplemaize, cotton, soya beans), KnockOut® (for example maize), StarLink®(for example maize), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf®(potato). Examples of herbicide-tolerant plants which may be mentionedare maize varieties, cotton varieties and soya bean varieties which aresold under the trade names Roundup Ready® (tolerance to glyphosate, forexample maize, cotton, soya bean), Liberty Link® (tolerance tophosphinotricin, for example oilseed rape), IMI® (tolerance toimidazolinones) and STS® (tolerance to sulphonylureas, for examplemaize). Herbicide-resistant plants (plants bred in a conventional mannerfor herbicide tolerance) which may be mentioned include the varietiessold under the name Clearfield® (for example maize). Of course, thesestatements also apply to plant cultivars having these or still to bedeveloped genetic traits, which plants will be developed and/or marketedin the future.

The plants listed can be treated according to the invention in aparticularly advantageous manner with the compounds of the generalformula I or the active compound mixtures according to the invention.The preferred ranges stated above for the active compounds or mixturesalso apply to the treatment of these plants. Particular emphasis isgiven to the treatment of plants with the compounds or the mixturesspecifically mentioned in the present text.

Treatment according to the invention of the plants and plant parts withthe active compounds is carried out directly or by allowing thecompounds to act on their surroundings, environment or storage space bythe customary treatment methods, for example by immersion, spraying,evaporation, fogging, scattering, painting on and, in the case ofpropagation material, in particular in the case of seed, also byapplying one or more coats.

The active compounds can be converted into the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,dusts, pastes, soluble powders, granules, suspension-emulsionconcentrates, natural and synthetic materials impregnated with activecompound, and microencapsulations in polymeric substances.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is liquid solvents and/orsolid carriers, optionally with the use of surfactants, that isemulsifiers and/or dispersants, and/or foam-formers.

If the extender used is water, it is also possible to employ for exampleorganic solvents as auxiliary solvents. Essentially, suitable liquidsolvents are: aromatics such as xylene, toluene or alkylnaphthalenes,chlorinated aromatics or chlorinated aliphatic hydrocarbons such aschlorobenzenes, chloroethylenes or methylene chloride, aliphatichydrocarbons such as cyclohexane or paraffins, for example petroleumfractions, mineral and vegetable oils, alcohols such as butanol orglycol and also their ethers and esters, ketones such as acetone, methylethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polarsolvents such as dimethylformamide and dimethyl sulphoxide, and alsowater.

As solid carriers there are suitable:

-   for example ammonium salts and ground natural minerals such as    kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or    diatomaceous earth, and ground synthetic minerals, such as highly    disperse silica, alumina and silicates; as solid carriers for    granules there are suitable: for example crushed and fractionated    natural rocks such as calcite, marble, pumice, sepiolite and    dolomite, and also synthetic granules of inorganic and organic    meals, and granules of organic material such as sawdust, coconut    shells, maize cobs and tobacco stalks; as emulsifiers and/or    foam-formers there are suitable: for example nonionic and anionic    emulsifiers, such as polyoxyethylene fatty acid esters,    polyoxyethylene fatty alcohol ethers, for example alkylaryl    polyglycol ethers, alkylsulphonates, alkyl sulphates,    arylsulphonates and also protein hydrolysates; as dispersants there    are suitable: for example lignin-sulphite waste liquors and    methylcellulose.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyes, such asalizarin dyes, azo dyes and metal phthalocyanine dyes, and tracenutrients such as salts of iron, manganese, boron, copper, cobalt,molybdenum and zinc.

The formulations generally comprise between 0.1 and 95% by weight ofactive compound, preferably between 0.5 and 90%.

The active compound according to the invention can be present in itscommercially available formulations and in the use forms, prepared fromthese formulations, as a mixture with other active compounds, such asinsecticides, attractants, sterilizing agents, bactericides, acaricides,nematicides, fungicides, growth-regulating substances or herbicides. Theinsecticides include, for example, phosphoric acid esters, carbamates,carboxylates, chlorinated hydrocarbons, phenylureas and substancesproduced by microorganisms, inter alia.

Particularly favourable examples of co-components in mixtures are thefollowing compounds:

Fungicides:

-   aldimorph, ampropylfos, ampropylfos-potassium, andoprim, anilazine,    azaconazole, azoxystrobin,-   benalaxyl, benodanil, benomyl, benzamacril, benzamacril-isobutyl,    bialaphos, binapacryl, biphenyl, bitertanol, blasticidin-S,    bromuconazole, bupirimate, buthiobate,-   calcium polysulphide, capsimycin, captafol, captan, carbendazim,    carboxin, carvon, quinomethionate, chlobenthiazone, chlorfenazole,    chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon,    cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuram,-   debacarb, dichlorophen, diclobutrazole, diclofluanid, diclomezine,    dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph,    diniconazole, diniconazole-M, dinocap, diphenylamine, dipyrithione,    ditalimfos, dithianon, dodemorph, dodine, drazoxolon,-   edifenphos, epoxiconazole, etaconazole, ethirimol, etridiazole,-   famoxadon, fenapanil, fenarimol, fenbuconazole, fenfuram,    fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate,    fentin hydroxide, ferbam, ferimzone, fluazinam, flumetover,    fluoromide, fluquinconazole, flurprimidol, flusilazole,    flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminium,    fosetyl-sodium, fthalide, fuberidazole, furalaxyl, furametpyr,    furcarbonil, furconazole, furconazole-cis, furmecyclox,-   guazatine,-   hexachlorobenzene, hexaconazole, hymexazole,-   imazalil, imibenconazole, iminoctadine, iminoctadine albesilate,    iminoctadine triacetate, iodocarb, ipconazole, iprobenfos (IBP),    iprodione, irumamycin, isoprothiolane, isovaledione,-   kasugamycin, kresoxim-methyl, copper preparations, such as: copper    hydroxide, copper naphthenate, copper oxychloride, copper sulphate,    copper oxide, oxine-copper and Bordeaux mixture,-   mancopper, mancozeb, maneb, meferimzone, mepanipyrim, mepronil,    metalaxyl, metconazole, methasulfocarb, methfuroxam, metiram,    metomeclam, metsulfovax, mildiomycin, myclobutanil, myclozolin,-   nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol,-   ofurace, oxadixyl, oxamocarb, oxolinic acid, oxycarboxim,    oxyfenthiin,-   paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphen,    pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz,    procymidone, propamocarb, propanosine-sodium, propiconazole,    propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon,    pyroxyfur,-   quinconazole, quintozene (PCNB),-   sulphur and sulphur preparations,-   tebuconazole, tecloftalam, tecnazene, tetcyclacis, tetraconazole,    thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram,    tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol,    triazbutil, triazoxide, trichlamide, tricyclazole, tridemorph,    triflumizole, triforine, triticonazole,-   uniconazole,-   validamycin A, vinclozolin, viniconazole,-   zarilamide, zineb, ziram and also-   Dagger G,-   OK-8705,-   OK-8801,-   α-(1,1-dimethylethyl)-β-(2-phenoxyethyl)-1H-1,2,4-triazole-1-ethanol,-   α-(2,4-dichlorophenyl)-β-fluoro-β-propyl-1H-1,2,4-triazole-1-ethanol,-   α-(2,4-dichlorophenyl)-β-methoxy-α-methyl-1H-1,2,4-triazole-1-ethanol,-   α-(5-methyl-1,3-dioxan-5-yl)-β-[[4-(trifluoromethyl)-phenyl]-methylene]-1H-1,2,4-triazole-1-ethanol,-   (5RS,6RS)-6-hydroxy-2,2,7,7-tetramethyl-5-(1H-1,2,4-triazol-1-yl)-3-octanone,-   (E)-α-(methoxyimino)-N-methyl-2-phenoxy-phenylacetamide,-   isopropyl    {2-methyl-1-[[[1-(4-methylphenyl)-ethyl]-amino]-carbonyl]-propyl}-carbamate,-   1-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-ethanone-O-(phenylmethyl)-oxime,-   1-(2-methyl-1-naphthalenyl)-1H-pyrrole-2,5-dione,-   1-(3,5-dichlorophenyl)-3-(2-propenyl)-2,5-pyrrolidinedione,-   1-[(diiodomethyl)-sulphonyl]-4-methyl-benzene,-   1-[[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl]-methyl]-1H-imidazole,-   1-[[2-(4-chlorophenyl)-3-phenyloxiranyl]-methyl]-1H-1,2,4-triazole,-   1-[1-[2-[(2,4-dichlorophenyl)-methoxy]-phenyl]-ethenyl]-1H-imidazole,-   1-methyl-5-nonyl-2-(phenylmethyl)-3-pyrrolidinol,-   2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoro-methyl-1,3-thiazole-5-carboxanilide,-   2,2-dichloro-N-[1-(4-chlorophenyl)-ethyl]-1-ethyl-3-methyl-cyclopropane-carboxamide,-   2,6-dichloro-5-(methylthio)-4-pyrimidinyl-thiocyanate,-   2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide,-   2,6-dichloro-N-[[4-(trifluoromethyl)-phenyl]-methyl]-benzamide,-   2-(2,3,3-triiodo-2-propenyl)-2H-tetrazole,-   2-[(1-methylethyl)-sulphonyl]-5-(trichloromethyl)-1,3,4-thiadiazole,-   2-[[6-deoxy-4-O-(4-O-methyl-β-D-glycopyranosyl)-α-D-glucopyranosyl]-amino]-4-methoxy-1H-pyrrolo[2,3-d]pyrimidine-5-carbonitrile,-   2-aminobutane,-   2-bromo-2-(bromomethyl)-pentanedinitrile,-   2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridinecarboxamide,-   2-chloro-N-(2,6-dimethylphenyl)-N-(isothiocyanatomethyl)-acetamide,-   2-phenylphenol (OPP),-   3,4-dichloro-1-[4-(difluoromethoxy)-phenyl]-1H-pyrrole-2,5-dione,-   3,5-dichloro-N-[cyano-[(1-methyl-2-propynyl)-oxy]-methyl]-benzamide,-   3-(1,1-dimethylpropyl)-1-oxo-1H-indene-2-carbonitrile,-   3-[2-(4-chlorophenyl)-5-ethoxy-3-isoxazolidinyl]-pyridine,-   4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulphonamide,-   4-methyl-tetrazolo[1,5-a]quinazolin-5(4H)-one,-   8-(1,1-dimethylethyl)-N-ethyl-N-propyl-1,4-dioxaspiro[4.5]decane-2-methanamine,-   8-hydroxyquinoline sulphate,-   9H-xanthene-2-[(phenylamino)-carbonyl]-9-carboxylic hydrazide,-   bis-(1-methylethyl)-3-methyl-4-[(3-methylbenzoyl)-oxy]-2,5-thiophene-dicarboxylate,-   cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol,-   cis-4-[3-[4-(1,1-dimethylpropyl)-phenyl-2-methylpropyl]-2,6-dimethyl-morpholinehydrochloride,-   ethyl [(4-chlorophenyl)-azo]-cyanoacetate,-   potassium hydrogen carbonate,-   methanetetrathiol sodium salt,-   methyl    1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate,-   methyl N-(2,6-dimethylphenyl)-N-(5-isoxazolylcarbonyl)-DL-alaninate,-   methyl N-(chloroacetyl)-N-(2,6-dimethylphenyl)-DL-alaninate,-   N-(2,3-dichloro-4-hydroxyphenyl)-1-methyl-cyclohexanecarboxamide,-   N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-furanyl)-acetamide,-   N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-thienyl)-acetamide,-   N-(2-chloro-4-nitrophenyl)-4-methyl-3-nitro-benzenesulfonamide,-   N-(4-cyclohexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidinamine,-   N-(4-hexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidinamine,-   N-(5-chloro-2-methylphenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)-acetamide,-   N-(6-methoxy)-3-pyridinyl)-cyclopropanecarboxamide,-   N-[2,2,2-trichloro-1-[(chloroacetyl)-amino]-ethyl]-benzamide,-   N-[3-chloro-4,5-bis-(2-propinyloxy)-phenyl]-N′-methoxy-methanimidamide,-   N-formyl-N-hydroxy-DL-alanine sodium salt,-   O,O-diethyl    [2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate,-   O-methyl S-phenyl phenylpropylphosphoramidothioate,-   S-methyl 1,2,3-benzothiadiazole-7-carbothioate,-   spiro[2H]-1-benzopyrane-2,1′(3′H)-isobenzofuran]-3′-one.

Bactericides:

-   bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,    kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin,    probenazole, streptomycin, tecloftalam, copper sulphate and other    copper preparations.

Insecticides/acaricides/nematicides:

-   abamectin, acephate, acetamiprid, acrinathrin, alanycarb, aldicarb,    aldoxycarb, alphacypermethrin, alphamethrin, amitraz, avermectin, AZ    60541, azadirachtin, azamethiphos, azinphos A, azinphos M,    azocyclotin,-   Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus    thuringiensis, Baculoviruses, Beauveria bassiana, Beauveria tenella,    bendiocarb, benfuracarb, bensultap, benzoximate, betacyfluthrin,    bifenazate, bifenthrin, bioethanomethrin, biopermethrin,    bistrifluron, BPMC, bromophos A, bufencarb, buprofezin, butathiofos,    butocarboxim, butylpyridaben,-   cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan,    cartap, chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos,    chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M,    chlovaporthrin, cis-resmethrin, cispermethrin, clocythrin,    cloethocarb, clofentezine, clothianidine, cyanophos, cycloprene,    cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin,    cyromazine,-   deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron,    diazinon, dichlorvos, diflubenzuron, dimethoate, dimethylvinphos,    diofenolan, disulfoton, docusat-sodium, dofenapyn,-   eflusilanate, emamectin, empenthrin, endosulfan, Entomopfthora spp.,    eprinomectin, esfenvalerate, ethiofencarb, ethion, ethoprophos,    etofenprox, etoxazole, etrimfos,-   fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion,    fenothiocarb, fenoxacrim, fenoxycarb, fenpropathrin, fenpyrad,    fenpyrithrin, fenpyroximate, fenvalerate, fipronil, fluazinam,    fluazuron, flubrocythrinate, flucycloxuron, flucythrinate,    flufenoxuron, flumethrin, flutenzine, fluvalinate, fonophos,    fosmethilan, fosthiazate, fubfenprox, furathiocarb,-   granulosis viruses,-   halofenozide, HCH, heptenophos, hexaflumuron, hexythiazox,    hydroprene,-   imidacloprid, indoxacarb, isazofos, isofenphos, isoxathion,    ivermectin, IKI 220,-   nuclear polyhedrosis viruses,-   lambda-cyhalothrin, lufenuron,-   malathion, mecarbam, metaldehyde, methamidophos, metharhizium    anisopliae, metharhizium flavoviride, methidathion, methiocarb,    methoprene, methomyl, methoxyfenozide, metolcarb, metoxadiazone,    mevinphos, milbemectin, milbemycin, monocrotophos,-   naled, nitenpyram, nithiazine, novaluron,-   omethoate, oxamyl, oxydemethon M,-   Paecilomyces fumosoroseus, parathion A, parathion M, permethrin,    phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim,    pirimicarb, pirimiphos A, pirimiphos M, profenofos, promecarb,    propoxur, prothiofos, prothoate, pymetrozine, pyraclofos,    pyresmethrin, pyrethrum, pyridaben, pyridathion, pyrimidifen,    pyriproxyfen,-   quinalphos,-   ribavirin,-   salithion, sebufos, selamectin, silafluofen, spinosad,    spirodiclofen, sulfotep, sulprofos, S 1812,-   tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimiphos,    teflubenzuron, tefluthrin, temephos, temivinphos, terbufos,    tetrachlorvinphos, thetacypermethrin, thiacloprid, thiamethoxam,    thiapronil, thiatriphos, thiocyclam hydrogen oxalate, thiodicarb,    thiofanox, thuringiensin, tralocythrin, tralomethrin, triarathene,    triazamate, triazophos, triazurone, trichlophenidine, trichlorfon,    triflumuron, trimethacarb,-   vamidothion, vaniliprole, Verticillium lecanii,-   YI 5302,-   zeta-cypermethrin, zolaprofos,-   (1R-cis)-[5-(phenylmethyl)-3-furanyl]-methyl-3-[(dihydro-2-oxo-3(2H)-furanyl-idene)-methyl]-2,2-dimethylcyclopropanecarboxylate,-   (3-phenoxyphenyl)-methyl-2,2,3,3-tetramethylcyclopropanecarboxylate,-   1-[(2-chloro-5-thiazolyl)methyl]tetrahydro-3,5-dimethyl-N-nitro-1,3,5-triazine-2(1H)-imine,-   2-(2-chloro-6-fluorophenyl)-4-[4-(1,1-dimethylethyl)phenyl]-4,5-dihydro-oxazole,-   2-(acetyloxy)-3-dodecyl-1,4-naphthalenedione,-   2-chloro-N-[[[4-(1-phenylethoxy)-phenyl]-amino]-carbonyl]-benzamide,-   2-chloro-N-[[[4-(2,2-dichloro-1,1-difluoroethoxy)-phenyl]-amino]-carbonyl]-benzamide,-   3-methylphenyl propylcarbamate,-   4-[4-(4-ethoxyphenyl)-4-methylpentyl]-1-fluoro-2-phenoxy-benzene,-   4-chloro-2-(1,1-dimethylethyl)-5-[[2-(2,6-dimethyl-4-phenoxyphenoxy)ethyl]thio]-3(2H)-pyridazinone,-   4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3-pyridinyl)methoxy]-3(2H)-pyridazinone,-   4-chloro-5-[(6-chloro-3-pyridinyl)methoxy]-2-(3,4-dichlorophenyl)-3(2H)-pyridazinone,-   Bacillus thuringiensis strain EG-2348,-   [2-benzoyl-1-(1,1-dimethylethyl)-hydrazinobenzoic acid,-   2,2-dimethyl-3-(2,4-dichlorophenyl)-2-oxo-1-oxaspiro[4.5]dec-3-en-4-yl    butanoate,-   [3-[(6-chloro-3-pyridinyl)methyl]-2-thiazolidinylidene]-cyanamide,-   dihydro-2-(nitromethylene)-2H-1,3-thiazine-3(4H)-carboxaldehyde,-   ethyl    [2-[[1,6-dihydro-6-oxo-1-(phenylmethyl)-4-pyridazinyl]oxy]ethyl]-carbamate,-   N-(3,4,4-trifluoro-1-oxo-3-butenyl)-glycine,-   N-(4-chlorophenyl)-3-[4-(difluoromethoxy)phenyl]-4,5-dihydro-4-phenyl-1H-pyrazole-1-carboxamide,-   N-[(2-chloro-5-thiazolyl)methyl]-N′-methyl-N″-nitro-guanidine,-   N-methyl-N′-(1-methyl-2-propenyl)-1,2-hydrazinedicarbothioamide,-   N-methyl-N′-2-propenyl-1,2-hydrazinedicarbothioamide,-   O,O-diethyl    [2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate.

A mixture with other known active compounds, such as herbicides, or withfertilizers and growth regulators is also possible.

The active compounds according to the invention can furthermore bepresent when used as insecticides in their commercially availableformulations and in the use forms, prepared from these formulations, asa mixture with synergistic agents. Synergistic agents are compoundswhich increase the action of the active compounds, without it beingnecessary for the synergistic agent added to be active itself.

The active compound content of the use forms prepared from thecommercially available formulations can vary within wide limits. Theactive compound concentration of the use forms can be from 0.0000001 to95% by weight of active compound, preferably between 0.0001 and 1% byweight.

The compounds are employed in a customary manner appropriate for the useforms.

When used against hygiene pests and pests of stored products, the activecompound is distinguished by an excellent residual action on wood andclay as well as a good stability to alkali on limed substrates.

The active compounds according to the invention act not only againstplant, hygiene and stored product pests, but also in the veterinarymedicine sector against animal parasites (ectoparasites), such as hardticks, soft ticks, mange mites, leaf mites, flies (biting and licking),parasitic fly larvae, lice, hair lice, feather lice and fleas. Theseparasites include:

From the order of the Anoplurida, for example, Haematopinus spp.,Linognathus spp., Pediculus spp., Phtirus spp. and Solenopotes spp.

From the order of the Mallophagida and the suborders Amblycerina andIschnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp.,Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp. and Felicola spp.

From the order Diptera and the suborders Nematocerina and Brachycerina,for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp.,Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp.,Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopotaspp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp.,Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossinaspp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp.,Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp.,Hippobosca spp., Lipoptena spp. and Melophagus spp.

From the order of the Siphonapterida, for example, Pulex spp.,Ctenocephalides spp., Xenopsylla spp. and Ceratophyllus spp.

From the order of the Heteropterida, for example, Cimex spp., Triatomaspp., Rhodnius spp. and Panstrongylus spp.

From the order of the Blattarida, for example, Blatta orientalis,Periplaneta americana, Blattela germanica and Supella spp.

From the subclass of the Acaria (Acarida) and the orders of the Meta-and Mesostigmata, for example, Argas spp., Ornithodorus spp., Otobiusspp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp.,Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp.,Raillietia spp., Pneumonyssus spp., Sternostoma spp. and Varroa spp.

From the order of the Actinedida (Prostigmata) and Acaridida(Astigmata), for example, Acarapis spp., Cheyletiella spp.,Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp.,Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.

The active compounds of the formula (I) according to the invention arealso suitable for controlling arthropods which infest agriculturalproductive livestock, such as, for example, cattle, sheep, goats,horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys,ducks, geese and bees, other pets, such as, for example, dogs, cats,caged birds and aquarium fish, and also so-called test animals, such as,for example, hamsters, guinea pigs, rats and mice. By controlling thesearthropods, cases of death and reduction in productivity (for meat,milk, wool, hides, eggs, honey etc.) should be diminished, so that moreeconomic and easier animal husbandry is possible by use of the activecompounds according to the invention.

The active compounds according to the invention are used in theveterinary sector in a known manner by enteral administration in theform of, for example, tablets, capsules, potions, drenches, granules,pastes, boluses, the feed-through process and suppositories, byparenteral administration, such as, for example, by injection(intramuscular, subcutaneous, intravenous, intraperitoneal and thelike), implants, by nasal administration, by dermal use in the form, forexample, of dipping or bathing, spraying, pouring on and spotting on,washing and powdering, and also with the aid of moulded articlescontaining the active compound, such as collars, ear marks, tail marks,limb bands, halters, marking devices and the like.

When used for cattle, poultry, pets and the like, the active compoundsof the formula (I) can be used as formulations (for example powders,emulsions, free-flowing compositions), which comprise the activecompounds in an amount of 1 to 80% by weight, directly or after 100 to10 000-fold dilution, or they can be used as a chemical bath.

The agents according to the invention are suitable for controllingpathogenic endoparasites encountered in humans and in animal husbandryand livestock breeding, in productive livestock, breeding stock, zooanimals, laboratory animals, animals used in experiments, and pets, andhave low toxicity towards warm-blooded animals. They are active againstall or some stages of development of the pests and against resistant andnormally sensitive species. By controlling the pathogenic endoparasites,it is intended to reduce disease, mortality and decreasing performance(for example in the production of meat, milk, wool, hides, eggs, honey,etc.), so that more economical and simpler animal keeping is possible byusing the active compounds. The pathogenic endoparasites includecestodes, trematodes, nematodes and acantocephales, in particular:

From the order of the Pseudophyllidea, for example Diphyllobothriumspp., Spirometra spp., Schistocephalus spp., Ligula spp., Bothridiumspp., Diphlogonoporus spp.

From the order of the Cyclophyllidea, for example Mesocestoides spp.,Anoplocephala spp., Paranoplocephala spp., Moniezia spp., Thysanosomsaspp., Thysaniezia spp., Avitellina spp., Stilesia spp., Cittotaeniaspp., Andyra spp., Bertiella spp., Taenia spp., Echinococcus spp.,Hydatigera spp., Davainea spp., Raillietina spp., Hymenolepis spp.,Echinolepis spp., Echinocotyle spp., Diorchis spp., Dipylidium spp.,Joyeuxiella spp., Diplopylidium spp.

From the subclass of the Monogenea, for example Gyrodactylus spp.,Dactylogyrus spp., Polystoma spp.

From the subclass of the Digenea, for example Diplostomum spp.,Posthodiplostomum spp., Schistosoma spp., Trichobilharzia spp.,Ornithobilharzia spp., Austrobilharzia spp., Gigantobilharzia spp.,Leucochloridium spp., Brachylaima spp., Echinostoma spp.,Echinoparyphium spp., Echinochasmus spp., Hypoderaeum spp., Fasciolaspp., Fasciolides spp., Fasciolopsis spp., Cyclocoelum spp.,Typhlocoelum spp., Paramphistomum spp., Calicophoron spp., Cotylophoronspp., Gigantocotyle spp., Fischoederius spp., Gastrothylacus spp.,Notocotylus spp., Catatropis spp., Plagiorchis spp., Prosthogonimusspp., Dicrocoelium spp., Eurytrema spp., Troglotrema spp., Paragonimusspp., Collyriclum spp., Nanophyetus spp., Opisthorchis spp., Clonorchisspp., Metorchis spp., Heterophyes spp., Metagonimus spp.

From the order of the Enoplida, for example Trichuris spp., Capillariaspp., Trichomosoides spp., Trichinella spp.

From the order of the Rhabditida, for example Micronema spp.,Strongyloides spp.

From the order of the Strongylida, for example Stronylus spp.,Triodontophorus spp., Oesophagodontus spp., Trichonema spp.,Gyalocephalus spp., Cylindropharynx spp., Poteriostomum spp.,Cyclococercus spp., Cylicostephanus spp., Oesophagostomum spp.,Chabertia spp., Stephanurus spp., Ancylostoma spp., Uncinaria spp.,Bunostomum spp., Globocephalus spp., Syngamus spp., Cyathostoma spp.,Metastrongylus spp., Dictyocaulus spp., Muellerius spp., Protostrongylusspp., Neostrongylus spp., Cystocaulus spp., Pneumostrongylus spp.,Spicocaulus spp., Elaphostrongylus spp., Parelaphostrongylus spp.,Crenosoma spp., Paracrenosoma spp., Angiostrongylus spp.,Aelurostrongylus spp., Filaroides spp., Parafilaroides spp.,Trichostrongylus spp., Haemonchus spp., Ostertagia spp., Marshallagiaspp., Cooperia spp., Nematodirus spp., Hyostrongylus spp., Obeliscoidesspp., Amidostomum spp., Ollulanus spp.

From the order of the Oxyurida, for example Oxyuris spp., Enterobiusspp., Passalurus spp., Syphacia spp., Aspiculuris spp., Heterakis spp.

From the order of the Ascaridia, for example Ascaris spp., Toxascarisspp., Toxocara spp., Parascaris spp., Anisakis spp., Ascaridia spp.

From the order of the Spirurida, for example Gnathostoma spp.,Physaloptera spp., Thelazia spp., Gongylonema spp., Habronema spp.,Parabronema spp., Draschia spp., Dracunculus spp.

From the order of the Filariida, for example Stephanofilaria spp.,Parafilaria spp., Setaria spp., Loa spp., Dirofilaria spp., Litomosoidesspp., Brugia spp., Wuchereria spp., Onchocerca spp.

From the order of the Gigantorhynchida, for example Filicollis spp.,Moniliformis spp., Macracanthorhynchus spp., Prosthenorchis spp.

The livestock and breeding stock include mammals, such as, for example,cattle, horses, sheep, pigs, goats, camels, water buffalo, donkeys,rabbits, fallow deer, reindeer, fur-bearing animals, such as, forexample, minks, chinchilla or racoon, birds, such as, for example,chickens, geese, turkeys, ducks or ostriches, freshwater fish and seafish, such as, for example, trout, carp and eels, reptiles and insects,such as, for example, honey bee and silkworm.

The laboratory and test animals include mice, rats, guinea pigs, goldenhamsters, dogs and cats.

The pets include dogs and cats.

Administration can be effected prophylactically as well astherapeutically.

The active substances are administered, either directly or in the formof suitable preparations, enterally, parenterally, dermally, nasally, bytreating the habitat or with the aid of shaped articles containing theactive compound, such as, for example, strips, plates, tapes, collars,ear tags, limb bands or marking devices.

Enteral administration of the active compounds is effected for exampleorally in the form of powders, tablets, capsules, pastes, drinks,granules, solutions, suspensions and emulsions which can be appliedorally, boluses, medicated feed or drinking water. Dermal application iseffected, for example, in the form of dipping, spraying, or pouring-onand spotting-on. Parenteral administration is effected, for example, inthe form of injection (intramuscular, subcutaneous, intravenous orintraperitoneal) or by implants.

Suitable preparations include:

Solutions, such as solutions for injection, oral solutions, concentratesfor oral administration after dilution, solutions for use on the skin orin body cavities, pour-on formulations, gels;

Emulsions and suspension for oral or dermal administration and forinjection; semi-solid preparations;

Formulations in which the active compound is incorporated in an ointmentbase or in an oil-in-water or water-in-oil emulsion base;

Solid preparations, such as powders, premixes or concentrates, granules,pellets, tablets, boluses, capsules; aerosols and inhalants, shapedarticles containing the active compound.

Solutions for injection are administered intravenously, intramuscularlyand subcutaneously. Solutions for injection are prepared by dissolvingthe active compound in a suitable solvent and, if desired, addingadditives, such as solubilizers, acids, bases, buffer salts,antioxidants, or preservatives. The solutions are sterile-filtered anddecanted into containers.

Suitable solvents include: physiologically acceptable solvents, such aswater, alcohols, such as ethanol, butanol, benzyl acohol, glycerol,propylene glycol, polyethylene glycols and N-methyl-pyrrolidone, andtheir mixtures.

If appropriate, the active compounds can also be dissolved inphysiologically acceptable vegetable or synthetic oils which aresuitable for injection.

Suitable solubilizers include: solvents which facilitate the dissolutionof the active compound in the main solvent or which preventprecipitation of the active compound. Examples of solubilizers arepolyvinylpyrrolidone, polyethoxylated castor oil and polyethoxylatedsorbitan esters.

The following are preservatives: benzyl alcohol, trichlorobutanol,p-hydroxybenzoic esters or n-butanol.

Oral solutions are administered directly. Concentrates are first dilutedto the administration concentration and then administered orally. Oralsolutions and concentrates are prepared as described above in the caseof the solutions for injection, sterile procedures not being necessary.

Solutions for use on the skin are applied drop by drop, smoothed on,rubbed in, splashed on or sprayed on. These solutions are prepared asdescribed above in the case of the solutions for injection.

It may be advantageous to add thickeners in the preparation process. Thefollowing are thickeners: inorganic thickeners, such as bentonites,colloidal silica, aluminium monostearate, or organic thickeners, such ascellulose derivatives, polyvinyl alcohols and their copolymers,acrylates and methacrylates.

Gels are applied to the skin or smoothed on or introduced into bodycavities. Gels are prepared by adding such an amount of thickener tosolutions which have been prepared as described for the solutions forinjection that a clear composition is formed which has an ointment-likeconsistency. The thickeners used are the thickeners indicated furtherabove.

Pour-on and spot-on formulations are poured or splashed onto limitedareas of the skin, the active compound penetrating the skin and actingsystemically.

Pour-on and spot-on formulations are prepared by dissolving, suspendingor emulsifying the active compound in suitable solvents or solventmixtures which are tolerated by the skin. If appropriate, otherauxiliaries, such as colorants, absorption promoters, antioxidants,photostabilizers or tackifiers are added.

Suitable solvents include: water, alkanols, glycols, polyethyleneglycols, polypropylene glycols, glycerol, aromatic alcohols, such asbenzyl alcohol, phenylethanol or phenoxyethanol, esters, such as ethylacetate, butyl acetate or benzyl benzoate, ethers, such as alkyleneglycol alkyl ethers, such as dipropylene glycol monomethyl ether ordiethylene glycol mono-butyl ether, ketones, such as acetone or methylethyl ketone, aromatic and/or aliphatic hydrocarbons, vegetable orsynthetic oils, DMF, dimethyl-acetamide, N-methylpyrrolidone, or2,2-dimethyl-4-oxy-methylene-1,3-dioxolane.

Colorants are all colorants which can be dissolved or suspended andwhich are approved for use in animals.

Examples of absorption promoters are DMSO, spreading oils, such asisopropyl myristate, dipropylene glycol pelargonate, silicone oils,fatty acid esters, triglycerides or fatty alcohols.

The following are antioxidants: sulfites or metabisulfites, such aspotassium metabisulfite, ascorbic acid, butylhydroxytoluene,butylhydroxyanisole or tocopherol.

Example of photostabilizers are novantisolic acid.

Tackifiers are, for example, cellulose derivatives, starch derivatives,polyacrylates or natural polymers such as alginates or gelatin.

Emulsions can be administered orally, dermally or as injections.

Emulsions are either the water-in-oil type or the oil-in-water type.

They are prepared by dissolving the active compound either in thehydrophobic or in the hydrophilic phase and by homogenizing this phasewith the solvent of the other phase, with the aid of suitableemulsifiers and, if appropriate, other auxiliaries, such as colorants,absorption promoters, preservatives, antioxidants, photostabilizers, andviscosity-increasing substances.

Suitable hydrophobic phases (oils) include: paraffin oils, siliconeoils, natural vegetable oils such as sesame seed oil, almond oil orcastor oil, synthetic triglycerides, such as caprylic/capric acidbiglyceride, a triglyceride mixture with vegetable fatty acids of chainlength C₈₋₁₂ or other specifically selected natural fatty acids,mixtures of partial glycerides of saturated or unsaturated fatty acidswhich may also contain hydroxyl groups, and mono- and diglycerides ofthe C₈/C₁₀-fatty acids.

Fatty acid esters, such as ethyl stearate, di-n-butyryl adipate, hexyllaurate, dipropylene glycol pelargonate, esters of a branched fatty acidhaving a medium chain length with saturated fatty alcohols of chainlength C₁₆-C₁₈, isopropyl myristate, isopropyl palmitate,caprylic/capric esters of saturated fatty alcohols of chain lengthC₁₂-C₁₈, isopropyl stearate, oleyl oleate, decyl oleate, ethyl oleate,ethyl lactate, waxy fatty acid esters such as artificial duck uropygialfat, dibutyl phthalate, diisopropyl adipate, ester mixtures related tothe latter, etc.

Fatty alcohols, such as isotridecyl alcohol, 2-octyldodecanol,cetylstearyl alcohol or oleyl alcohol.

Fatty acids, such as, for example, oleic acid and its mixtures.

Suitable hydrophilic phases include:

-   water, alcohols, such as, for example, propylene glycol, glycerol,    sorbitol and their mixtures.

Suitable emulsifiers include: nonionic surfactants, for examplepolyethoxylated castor oil, polyethoxylated sorbitan monooleate,sorbitan monostearate, glycerol monostearate, polyoxyethyl stearate oralkylphenol polyglycol ethers;

Ampholytic surfactants, such as disodium N-lauryl-β-iminodipropionate orlecithin;

Anionic surfactants, such as Na lauryl sulfate, fatty alcohol ethersulfates, and the monoethanolamine salt of mono/dialkylpolyglycol etherorthophosphoric ester;

Cation-active surfactants such as cetyltrimethylammonium chloride.

Suitable other auxiliaries include: substances which increase theviscosity and stabilize the emulsion, such as carboxymethylcellulose,methylcellulose and other cellulose and starch derivatives,polyacrylates, alginates, gelatin, gum arabic, polyvinylpyrrolidone,polyvinyl alcohol, methylvinyl ether/maleic anhydride copolymers,polyethylene glycols, waxes, colloidal silica, or mixtures of the listedsubstances.

Suspensions can be administered orally, dermally or as an injection.They are prepared by suspending the active compound in a liquidexcipient, if appropriate with the addition of other auxiliaries, suchas wetting agents, colorants, absorption promoters, preservatives,antioxidants and photostabilizers.

Suitable liquid excipients include all homogeneous solvents and solventmixtures.

Suitable wetting agents (dispersants) include the surfactants indicatedfurther above.

Suitable other auxiliaries include those indicated further above.

Semi-solid preparations can be administered orally or dermally. They areonly distinguished from the above-described suspensions and emulsions bytheir higher viscosity.

To prepare solid preparations, the active compound is mixed withsuitable excipients, if appropriate with the addition of auxiliaries,and the mixture is formulated as desired.

Suitable excipients include all physiologically acceptable solid inertsubstances. Suitable for this purpose are inorganic and organicsubstances. Inorganic substances are, for example, common salt,carbonates, such as calcium carbonate, hydrogen carbonates, aluminiumoxides, silicas, clays, precipitated or colloidal silica, andphosphates.

Organic substances are, for example, sugars, cellulose, foodstuffs andanimal feeds, such as powdered milk, animal meals, cereal meals, coarsecereal meals and starches.

Auxiliaries are preservatives, antioxidants and colorants which havealready been mentioned further above.

Other suitable auxiliaries are lubricants and glidants, such as, forexample, magnesium stearate, stearic acid, talc, bentonites,disintegrants, such as starch or crosslinked polyvinylpyrrolidone,binders, such as, for example, starch, gelatin or linearpolyvinylpyrrolidone, and dry binders, such as microcrystallinecellulose.

In the preparations, the active compounds can also be present inmixtures with synergists or other active compounds which are activeagainst pathogenic endoparasites. Examples of such active compounds areL-2,3,5,6-tetrahydro-6-phenyl-imidazothiazole, benzimidazole carbamatesor pyrantel.

Ready-to-use preparations contain the active compounds in concentrationsof 10 ppm to 20 percent by weight, preferably from 0.1 to 10 percent byweight.

Preparations which are diluted before use contain the active compoundsin concentrations of 0.5 to 90 percent by weight, preferably from 5 to50 percent by weight.

In general it has been found to be advantageous to administer themixture according to the invention in amounts of from about 10 to about100 mg of active compound per kg of body weight per day to obtain goodresults. Preference is given to using from 10 to 50 mg of activecompound mixture per kg of body weight.

In the compositions, the weight ratio of praziquantel and/or epsiprantelto depsipeptide is generally 1:1-10, preferably 1:1-2 and veryparticularly preferably 1:1.

It has furthermore been found that the compounds according to theinvention also have a strong insecticidal action against insects whichdestroy industrial materials.

The following insects may be mentioned as examples and as beingpreferred—but without any limitation:

Beetles, such as

-   Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum,    Xestobium rufovillosum, Ptilinus pecticomis, Dendrobium pertinex,    Emobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus,    Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon    aequale, Minthes rugicollis, Xyleborus spec., Tryptodendron spec.,    Apate monachus, Bostrychus capucins, Heterobostrychus brunneus,    Sinoxylon spec. and Dinoderus minutus.

Hymenopterons, such as

-   Sirex juvencus, Urocerus gigas, Urocerus gigas taignus and Urocerus    augur.

Termites, such as

-   Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola,    Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes    lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis and    Coptotermes formosanus.

Bristletails, such as Lepisma saccharina.

Industrial materials in the present context are to be understood asmeaning non-living materials, such as, preferably, plastics, adhesives,sizes, papers and cards, leather, wood and processed wood products andcoating compositions.

Wood and processed wood products are materials to be protected,especially preferably, from insect infestation.

Wood and processed wood products which can be protected by the agentaccording to the invention or mixtures comprising this are to beunderstood as meaning, for example:

-   building timber, wooden beams, railway sleepers, bridge components,    boat jetties, wooden vehicles, boxes, pallets, containers, telegraph    poles, wood panelling, wooden windows and doors, plywood, chipboard,    joinery or wooden products which are used quite generally in    house-building or in building joinery.

The active compounds can be used as such, in the form of concentrates orin generally customary formulations, such as powders, granules,solutions, suspensions, emulsions or pastes.

The formulations mentioned can be prepared in a manner known per se, forexample by mixing the active compounds with at least one solvent ordiluent, emulsifier, dispersing agent and/or binder or fixing agent, awater repellent, if appropriate siccatives and UV stabilizers and ifappropriate dyes and pigments, and also other processing auxiliaries.

The insecticidal compositions or concentrates used for the preservationof wood and wood-derived timber products comprise the active compoundaccording to the invention in a concentration of 0.0001 to 95% byweight, in particular 0.001 to 60% by weight.

The amount of the compositions or concentrates employed depends on thenature and occurrence of the insects and on the medium. The optimumamount employed can be determined for the use in each case by a seriesof tests. In general, however, it is sufficient to employ 0.0001 to 20%by weight, preferably 0.001 to 10% by weight, of the active compound,based on the material to be preserved.

Solvents and/or diluents which are used are an organic chemical solventor solvent mixture and/or an oily or oil-like organic chemical solventor solvent mixture of low volatility and/or a polar organic chemicalsolvent or solvent mixture and/or water, and if appropriate anemulsifier and/or wetting agent.

Organic chemical solvents which are preferably used are oily or oil-likesolvents having an evaporation number above 35 and a flashpoint above30° C., preferably above 45° C. Substances which are used as such oilyor oil-like water-insoluble solvents of low volatility are appropriatemineral oils or aromatic fractions thereof, or solvent mixturescontaining mineral oils, preferably white spirit, petroleum and/oralkylbenzene.

Mineral oils having a boiling range from 170 to 220° C., white spirithaving a boiling range from 170 to 220° C., spindle oil having a boilingrange from 250 to 350° C., petroleum and aromatics having a boilingrange from 160 to 280° C., turpentine oil and the like, areadvantageously employed.

In a preferred embodiment, liquid aliphatic hydrocarbons having aboiling range from 180 to 210° C. or high-boiling mixtures of aromaticand aliphatic hydrocarbons having a boiling range from 180 to 220° C.and/or spindle oil and/or monochloronaphthalene, preferablyα-monochloronaphthalene, are used.

The organic oily or oil-like solvents of low volatility which have anevaporation number above 35 and a flashpoint above 30° C., preferablyabove 45° C., can be replaced in part by organic chemical solvents ofhigh or medium volatility, providing that the solvent mixture likewisehas an evaporation number above 35 and a flashpoint above 30° C.,preferably above 45° C., and that the insecticide/fungicide mixture issoluble or emulsifiable in this solvent mixture.

According to a preferred embodiment, some of the organic chemicalsolvent or solvent mixture is replaced by a polar organic chemicalsolvent or solvent mixture. Organic chemical solvents containinghydroxyl and/or ester and/or ether groups, such as, for example, glycolethers, esters or the like, are preferably used.

Organic chemical binders which are used in the context of the presentinvention are the synthetic resins and/or binding drying oils which areknown per se, are water-dilutable and/or are soluble or dispersible oremulsifiable in the organic chemical solvents employed, in particularbinders consisting of or comprising an acrylate resin, a vinyl resin,for example polyvinyl acetate, polyester resin, polycondensation orpolyaddition resin, polyurethane resin, alkyd resin or modified alkydresin, phenolic resin, hydrocarbon resin, such as indene-cumarone resin,silicone resin, drying vegetable oils and/or drying oils and/orphysically drying binders based on a natural and/or synthetic resin.

The synthetic resin used as the binder can be employed in the form of anemulsion, dispersion or solution. Bitumen or bituminous substances canalso be used as binders in an amount of up to 10% by weight. Dyestuffs,pigments, water-repelling agents, odour correctants and inhibitors oranticorrosive agents and the like which are known per se canadditionally be employed.

It is preferred according to the invention for the composition orconcentrate to comprise, as the organic chemical binder, at least onealkyd resin or modified alkyd resin and/or one drying vegetable oil.Alkyd resins having an oil content of more than 45% by weight,preferably 50 to 68% by weight, are preferably used according to theinvention.

All or some of the binder mentioned can be replaced by a fixing agent(mixture) or a plasticizer (mixture). These additives are intended toprevent evaporation of the active compounds and crystallization orprecipitation. They preferably replace 0.01 to 30% of the binder (basedon 100% of the binder employed).

The plasticizers originate from the chemical classes of phthalic acidesters, such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoricacid esters, such as tributyl phosphate, adipic acid esters, such asdi-(2-ethylhexyl) adipate, stearates, such as butyl stearate or amylstearate, oleates, such as butyl oleate, glycerol ethers or highermolecular weight glycol ethers, glycerol esters and p-toluenesulphonicacid esters.

Fixing agents are based chemically on polyvinyl alkyl ethers, such as,for example, polyvinyl methyl ether or ketones, such as benzophenone orethylenebenzophenone.

Possible solvents or diluents are, in particular, also water, ifappropriate as a mixture with one or more of the abovementioned organicchemical solvents or diluents, emulsifiers and dispersing agents.

Particularly effective preservation of wood is achieved by impregnationprocesses on a large industrial scale, for example vacuum, double vacuumor pressure processes.

The ready-to-use compositions can also comprise other insecticides, ifappropriate, and also one or more fungicides, if appropriate.

Possible additional mixing partners are, preferably, the insecticidesand fungicides mentioned in WO 94/29 268. The compounds mentioned inthis document are an explicit constituent of the present application.

Especially preferred mixing partners which may be mentioned areinsecticides, such as chlorpyriphos, phoxim, silafluofin, alphamethrin,cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25,flufenoxuron, hexaflumuron, transfluthrin, thiacloprid, methoxyphenoxideand triflumuron,

and also fungicides, such as epoxyconazole, hexaconazole, azaconazole,propiconazole, tebuconazole, cyproconazole, metconazole, imazalil,dichlorfluanid, tolylfluanid, 3-iodo-2-propinyl-butyl carbamate,N-octyl-isothiazolin-3-one and 4,5-dichloro-N-octylisothiazolin-3-one.

The compounds according to the invention can at the same time beemployed for protecting objects which come into contact with salt wateror brackish water, such as hulls, screens, nets, buildings, moorings andsignalling systems, against fouling.

Fouling by sessile Oligochaeta, such as Serpulidae, and by shells andspecies from the Ledamorpha group (goose barnacles), such as variousLepas and Scalpellum species, or by species from the Balanomorpha group(acorn barnacles), such as Balanus or Pollicipes species, increases thefrictional drag of ships and, as a consequence, leads to a markedincrease in operation costs owing to higher energy consumption andadditionally frequent residence in the dry dock.

Apart from fouling by algae, for example Ectocarpus sp. and Ceramiumsp., fouling by sessile Entomostraka groups, which come under thegeneric term Cirripedia (cirriped crustaceans), is of particularimportance.

Surprisingly, it has now been found that the compounds according to theinvention, alone or in combination with other active compounds, have anoutstanding antifouling action.

Using the compounds according to the invention, alone or in combinationwith other active compounds, allows the use of heavy metals such as, forexample, in bis-(trialkyltin) sulphides, tri-n-butyltin laurate,tri-n-butyltin chloride, copper(I) oxide, triethyltin chloride,tri-n-butyl(2-phenyl-4-chlorophenoxy)tin, tributyltin oxide, molybdenumdisulphide, antimony oxide, polymeric butyl titanate,phenyl(bispyridine)-bismuth chloride, tri-n-butyltin fluoride, manganeseethylenebisthiocarbamate, zinc dimethyldithiocarbamate, zincethylenebisthiocarbamate, zinc salts and copper salts of 2-pyridinethiol1-oxide, bisdimethyldithiocarbamoylzinc ethylene-bisthiocarbamate, zincoxide, copper(I) ethylene-bisdithiocarbamate, copper thiocyanate, coppernaphthenate and tributyltin halides to be dispensed with, or theconcentration of these compounds substantially reduced.

If appropriate, the ready-to-use antifouling paints can additionallycomprise other active compounds, preferably algicides, fungicides,herbicides, molluscicides, or other antifouling active compounds.

Preferably suitable components in combinations with the antifoulingcompositions according to the invention are:

-   algicides such as-   2-tert-butylamino-4-cyclopropylamino-6-methylthio-1,3,5-triazine,    dichlorophen, diuron, endothal, fentin acetate, isoproturon,    methabenzthiazuron, oxyfluorfen, quinoclamine and terbutryn;-   fungicides such as-   benzo[b]thiophenecarboxylic acid cyclohexylamide S,S-dioxide,    dichlofluanid, fluorfolpet, 3-iodo-2-propinyl butylcarbamate,    tolylfluanid and azoles such as-   azaconazole, cyproconazole, epoxyconazole, hexaconazole,    metconazole, propiconazole and tebuconazole;-   molluscicides such as-   fentin acetate, metaldehyde, methiocarb, niclosamid, thiodicarb and    trimethacarb;-   or conventional antifouling active compounds such as-   4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethylparatryl    sulphone, 2-(N,N-dimethylthiocarbamoylthio)-5-nitrothiazyl,    potassium, copper, sodium and zinc salts of 2-pyridinethiol 1-oxide,    pyridine-triphenylborane, tetrabutyldistannoxane,    2,3,5,6-tetrachloro-4-(methylsulphonyl)-pyridine,    2,4,5,6-tetrachloroisophthalonitrile, tetramethylthiuram disulphide    and 2,4,6-trichlorophenylmaleimide.

The antifouling compositions used comprise the active compound accordingto the invention of the compounds according to the invention in aconcentration of 0.001 to 50% by weight, in particular 0.01 to 20% byweight.

Moreover, the antifouling compositions according to the inventioncomprise the customary components such as, for example, those describedin Ungerer, Chem. Ind. 1985, 37, 730-732 and Williams, AntifoulingMarine Coatings, Noyes, Park Ridge, 1973.

Besides the algicidal, fungicidal, molluscicidal active compounds andinsecticidal active compounds according to the invention, antifoulingpaints comprise, in particular, binders.

Examples of recognized binders are polyvinyl chloride in a solventsystem, chlorinated rubber in a solvent system, acrylic resins in asolvent system, in particular in an aqueous system, vinyl chloride/vinylacetate copolymer systems in the form of aqueous dispersions or in theform of organic solvent systems, butadiene/styrene/acrylonitrilerubbers, drying oils such as linseed oil, resin esters or modifiedhardened resins in combination with tar or bitumens, asphalt and epoxycompounds, small amounts of chlorine rubber, chlorinated polypropyleneand vinyl resins.

If appropriate, paints also comprise inorganic pigments, organicpigments or colorants which are preferably insoluble in salt water.Paints may furthermore comprise materials such as colophonium to allowcontrolled release of the active compounds. Furthermore, the paints maycomprise plasticizers, modifiers which affect the rheological propertiesand other conventional constituents. The compounds according to theinvention or the abovementioned mixtures may also be incorporated intoself-polishing antifouling systems.

The active compounds are also suitable for controlling animal pests, inparticular insects, arachnids and mites, which are found in enclosedspaces such as, for example, dwellings, factory halls, offices, vehiclecabins and the like. They can be employed in domestic insecticideproducts for controlling these pests alone or in combination with otheractive compounds and auxiliaries. They are active against sensitive andresistant species and against all developmental stages. These pestsinclude:

From the order of the Scorpionidea, for example, Buthus occitanus.

From the order of the Acarina, for example, Argas persicus, Argasreflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus,Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi,Neutrombicula autumnalis, Dermatophagoides pteronissimus,Dermatophagoides forinae.

From the order of the Araneae, for example, Aviculariidae, Araneidae.

From the order of the Opiliones, for example, Pseudoscorpiones chelifer,Pseudoscorpiones cheiridium, Opiliones phalangium.

From the order of the Isopoda, for example, Oniscus asellus, Porcellioscaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus,Polydesmus spp.

From the order of the Chilopoda, for example, Geophilus spp.

From the order of the Zygentoma, for example, Ctenolepisma spp., Lepismasaccharina, Lepismodes inquilinus.

From the order of the Blattaria, for example, Blatta orientalies,Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchloraspp., Parcoblatta spp., Periplaneta australasiae, Periplaneta americana,Periplaneta brunnea, Periplaneta fuliginosa, Supella longipalpa.

From the order of the Saltatoria, for example, Acheta domesticus.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Kalotermes spp.,Reticulitermes spp.

From the order of the Psocoptera, for example, Lepinatus spp.,Liposcelis spp.

From the order of the Coleptera, for example, Anthrenus spp., Attagenusspp., Dermestes spp., Latheticus oryzae, Necrobia spp., Ptinus spp.,Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae,Sitophilus zeamais, Stegobium paniceum.

From the order of the Diptera, for example, Aedes aegypti, Aedesalbopictus, Aedes taeniorhynchus, Anopheles spp., Calliphoraerythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culexpipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Muscadomestica, Phlebotomus spp., Sarcophaga camaria, Simulium spp., Stomoxyscalcitrans, Tipula paludosa.

From the order of the Lepidoptera, for example, Achroia grisella,Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tineapellionella, Tineola bisselliella.

From the order of the Siphonaptera, for example, Ctenocephalides canis,Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsyllacheopis.

From the order of the Hymenoptera, for example, Camponotus herculeanus,Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis,Paravespula spp., Tetramorium caespitum.

From the order of the Anoplura, for example, Pediculus humanus capitis,Pediculus humanus corporis, Phthirus pubis.

From the order of the Heteroptera, for example, Cimex hemipterus, Cimexlectularius, Rhodinus prolixus, Triatoma infestans.

They are used in the household insecticides sector alone or incombination with other suitable active compounds such as phosphoricesters, carbamates, pyrethroids, growth regulators or active compoundsfrom other known classes of insecticides.

They are used in aerosols, pressure-free spray products, for examplepump and atomizer sprays, automatic fogging systems, foggers, foams,gels, evaporator products with evaporator tablets made of cellulose orpolymer, liquid evaporators, gel and membrane evaporators,propeller-driven evaporators, energy-free, or passive, evaporationsystems, moth papers, moth bags and moth gels, as granules or dusts, inbaits for spreading or in bait stations.

PREPARATION EXAMPLES Example 1

(Process a)

4.7 g (34 mmol) of potassium carbonate and then 2.7 g (12.7 mmol) of6,6,5-trifluorohex-5-enyl bromide are added to a solution of 2.8 g (11.4mmol) of 2-mercapto-5-(4-trifluoromethylphenyl)-1,3,4-oxadiazole in 30ml of acetonitrile. The reaction mixture is heated at reflux for 6 hoursand then poured into water and extracted with dichloromethane. Removalof the solvent gives 4.7 g of crude product which are purified on silicagel using the system dichloromethane/ethyl acetate (4:1).

This gives 3.2 g (73.4% of theory) of2-(6,6,5-trifluorohex-5-enylthio)-5-(4-trifluoromethyl-phenyl)-1,3,4-oxadiazoleof melting point 40° C.

The compounds of formula (I) listed in Tables 1 and 2 below are obtainedsimilarly to Example 1 and/or in accordance with the general statementson the preparation:

TABLE 1 (IB)

Ex. logP (pH2) No. R¹ Y n m X or NMR 2

O 0 4 H 4.77 3

O 0 4 F 3.97 4

O 0 4 H 4.08 5 CH₃S— S 0 4 F 3.69 6 CH₃S— S 0 4 H 3.79 7

O 0 4 F 3.74 8

O 0 4 H 3.84 9 CH₃S(O)— S 0 4 F 2.46 10 CF₃— S 0 4 H 4.32 11 CF₃— S 0 4F 4.21 12 (CH₃)₂CH(CH₂)₂S— S 0 4 H 5.68 13 (CH₃)₂CH(CH₂)₂S— S 0 4 F 5.5314

O 0 4 F 3.90 15

O 0 4 F 4.55 16

O 0 4 F 4.55 17 ClCH₂CH₂S— S 0 4 F 4.28 18

S 0 4 F 4.95 19

S 0 4 F 5.05 20 HS— S 0 4 F ¹H-NMR in CDCl₃/ δ in ppm: 3.3(2H);2.35(2H); 1.75(2H) 21 CF₂═CF—(CH₂)₄—S— S 0 4 F 5.27 22

O 0 4 H 4.68 23 ClCH₂CH₂S— S 0 4 H 4.40 24 C₂H₅O— S 0 4 F 3.80 25i-C₃H₇O— S 0 4 F 4.24 26

S 0 4 H 5.19 27 F₂C═CF—(CH₂)₂—S— S O 4 F 4.71 28 F₂C═CF—(CH₂)₂—S— S O 4H 4.84 29 F₂CH—S— S O 4 F 3.82 30 F₂CH—S— S O 4 H 3.91

TABLE 2 (IC)

Ex. No. R² n m X logP (pH 2) IB-1 H O 4 H 1.48 IB-2 H O 4 F 1.51

The logP values were determined in accordance with EEC Directive 79/831Annex V.A8 by HPLC (gradient method, acetonitrile/0.1% aqueousphosphoric acid).

Example A

Meloidogyne Test

Solvent: 30 parts by weight of dimethylformamide or 4 parts by weight ofacetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

Containers are filled with sand, solution of active compound,Meloidogyne incognita egg/larvae suspension and lettuce seeds. Thelettuce seeds germinate and the plants develop. On the roots, galls areformed.

After the desired period of time, the nematicidal action is determinedin % using gall formation as a measure. 100% means that no galls werefound; 0% means that the number of galls on the treated plantscorresponds to that of the untreated control.

In this test, for example, at an exemplary active compound concentrationof 20 ppm, the compounds of Preparation Examples 2, 4, 5, 7, 8, 12, 13,14, 15 and 19 exhibit an activity of 100% and the compound ofPreparation Example 18 exhibits an activity of 90%, in each case after14 days.

Example B

Myzus Test

Solvent: 30 parts by weight of dimethylformamide Emulsifier: 1 part byweight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted withemulsifier-containing water to the desired concentrations.

Broad bean (Vicia faba) seedlings which are infested by the peach aphid(Myzus persicae) are dipped into the preparation of active compound ofthe desired concentration and put into a plastic box.

After the desired period of time, the kill in % is determined. 100%means that all animals have been killed; 0% means that none of theanimals have been killed.

In this test, for example, at an exemplary active compound concentrationof 10 ppm, the compounds of Preparation Examples 2 and 6 effect a killof 95%, the compound of Preparation Example 7 a kill of 89% and thecompounds of Preparation Examples 8 and 10 a kill of 100%, in each caseafter 6 days.

Example C

Phaedon Larvae Test

Solvent: 30 parts by weight of dimethylformamide Emulsifier: 1 part byweight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with larvae of the mustard beetle (Phaedon cochleariae) whilethe leaves are still moist.

After the desired period of time, the kill in % is determined. 1000 ppmmeans that all beetle larvae have been killed; 0% means that none of thebeetle larvae have been killed.

In this test, for example, at an exemplary active compound concentrationof 1000 ppm, the compounds of Preparation Examples 2, 4, 6, 11, 12, 15,18 and 19 effect a kill of 100% after 7 days.

Example D

Spodoptera frugiperda Test

Solvent: 30 parts by weight of dimethylformamide Emulsifier: 1 part byweight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with caterpillars of the army worm (Spodoptera frugiperda)while the leaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all caterpillars have been killed; 0% means that none of thecaterpillars have been killed.

In this test, for example, at an exemplary active compound concentrationof 1000 ppm, the compounds of Preparation Examples 1 and 10 effect akill of 100% after 7 days.

Example E

Tetranychus Test (OP-resistant/Dip Treatment)

Solvent: 30 parts by weight of dimethylformamide Emulsifier: 1 part byweight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Bean plants (Phaseolus vulgaris) which are heavily infested by allstages of the greenhouse red spider mite (Tetranychus urticae) aredipped into a preparation of active compound of the desiredconcentration.

After the desired period of time, the kill in % is determined. 100%means that all spider mites have been killed; 0% means that none of thespider mites have been killed.

In this test, for example, at an exemplary active compound concentrationof 0.1%, the compound of Preparation Example 6 effects a kill of 98% andthe compounds of Preparation Examples 2, 4, 8 and 12 effect a kill of98%, in each case after 7 days.

Example F

Test with Boophilus microplus Resistant (SP-resistant ParkhurstStrain/I)

Test animals: adult females which have sucked themselves full Solvent:dimethyl sulphoxide

20 mg of active compound are dissolved in 1 ml of dimethyl sulphoxide,more dilute concentrations are prepared by dilution with distilledwater.

10 adult Boophilus microplus res. are dipped for 1 minute into thepreparation of active compound to be tested. The animals are transferredinto plastic beakers and kept in a climatized room, and the kill rate isthen determined.

100% means that all tics have been killed; 0% means that none of thetics have been killed.

In this test, for example, at an exemplary active compound concentrationof 100 ppm, the compounds of Preparation Examples 6, 10 and 12 eacheffect a kill of 100%.

Example G

Test with Boophilus microplus Resistant (SP-resistant ParkhurstStrain/II)

Test animals: adult females which have sucked themselves full Solvent:dimethyl sulphoxide

20 mg of active compound are dissolved in 1 ml of dimethyl sulphoxide,more dilute concentrations are prepared by dilution in the same solvent.

The test is carried out in 5 replications. 1 μl of the solutions isinjected into the abdomen, and the animals are transferred into dishesand kept in a climatized room. After 7 days, the activity is checked byexamination for oviposition of fertile eggs. Eggs whose fertility is notvisible from the outside are stored in glass tubes in acontrolled-environment cabinet until the larvae have hatched. Anactivity of 100% means that no tick has produced any fertile eggs.

In this test, for example, at an exemplary amount of active compound of20 μg per animal, the compounds of Preparation Examples 2, 5, 6, 8, 10,12, 17 and 21 each effect a kill of 100%. At an amount of activecompound of 4 and 0.8 μg per animal, for example, the compounds ofPreparation Examples 6, 8, 10, 12, 17 and 21 each exhibit an activity of100%.

Example H

Blowfly Larvae Test/Development-inhibitory Action

Test animals: Lucilia cuprina larvae Solvent: dimethyl sulphoxide

20 mg of active compound are dissolved in 1 ml of dimethyl sulphoxide,more dilute concentrations are prepared by dilution with distilledwater.

About 20 Lucilia cuprina larvae are introduced into a test tube whichcontains about 1 cm³ of horse meat and 0.5 ml of the preparation ofactive compound to be tested. After 24 hours and 48 hours, the efficacyof the preparation of active compound is determined. The test tubes aretransferred into a beaker whose bottom is covered with sand. After afurther 2 days, the test tubes are removed and the pupae are counted.

The efficacy of the preparation of active compound is assessed by thenumber of flies that have hatched after 1.5 times the period ofdevelopment of an untreated control. 100% means that no flies havehatched; 0% means that all flies have hatched normally.

In this test, at an exemplary active compound concentration of 100 ppm,the compounds of Preparation Examples 8 and 12 effect a kill of 100%.

Example J

Cockroach Test

Test animals: Blatella germanica or Periplaneta americana Solvent:dimethyl sulphoxide

20 mg of active compound are dissolved in 1 ml of dimethyl sulphoxide,more dilute concentrations are prepared by dilution with distilled H₂O.

4 test animals are dipped for 1 minute into the preparation of activecompound to be tested.

The test animals are transferred into plastic beakers and kept in aclimatized room for 7 days, after which the kill rate is determined.

100% means that all cockroaches have been killed, 0% means that none ofthe cockroaches have been killed.

In this test, at an exemplary active compound concentration of 100 ppm,the compounds of Preparation Examples 8 and 10 each effect a kill of100%, the compound of Preparation Example 6 effects a kill of 75%.

Example K

Test with Cat Fleas/Oral Uptake

Test animals: adults of Ctenocephalides felis Solvent: dimethylsulphoxide (DMSO)

To produce a suitable formulation, a suitable solution of activecompound is prepared from 20 mg of active compound and 1 ml of DMSO. 15μl of this formulation are added to 3 ml of citrated cattle blood andstirred.

10 unfed adult fleas (Ctenocephalides felis, strain “Georgi”) are placedinto a chamber (Ø 3.2 cm) whose top and bottom are closed with gauze. Ametal cylinder whose underside is covered with parafilm is placed ontothe chamber. The cylinder contains 3 ml of blood/active compoundformulation which can be taken up by the fleas through the parafilmmembrane. Whereas the blood is warmed to 37° C., the temperature in thearea of the flea chambers is adjusted to 25° C. Controls are mixed withthe same volume of DMSO, without addition of a compound. Thedeterminations are carried out in triplicate.

After 28 h, the mortality in % (=dead fleas) is determined.

Compounds which effect an at least 25% kill of the fleas within 28 h arejudged to be effective.

In this test, at an exemplary active compound concentration of 100 ppm,the compounds of Preparation Examples 2, 6, 8, 10, 12 and 15 effected akill of 93, 81, 72, 87, 94 and 57%, respectively.

Example L

Nippostrongylus brasiliensis In-vitro

Test animals: adult Nippostrongylus brasiliensis Solvent: dimethylsuiphoxide

Nippostrongylus brasiliensis worms are isolated from the small intestineof female Wistar rats and collected in aqueous 0.9% NaCl containing 20μg of sisomycin/ml and 2 μg of Canesten/ml. The incubation of the twogroups of worms (of male/female sex) is carried out in 1.0 ml of medium,which is used for determining the acetylcholinesterase activity.Incubation conditions and the determination of the enzyme activity aredescribed in Martin et al., Pesticide Science (1996) 48, 343-349. Thecompounds are dissolved in the stated solvent (10 mg per 0.5 ml) anddiluted to the desired concentration. The controls contain only thesolvent.

The vitality of the worms is characterized by the acetylcholinesteraseactivity which the worms have secreted actively into the incubationmedium. The acetylcholinesterase acivity is classified in accordancewith the abovementioned work by Martin et al. (1996). 0 means noactivity, 1 means weak activity, 2 means good activity and 3 means fullactivity (<50%, 50-75%, >75%, 100% enzyme inhibition).

In this test, for example, at an exemplary active compound concentrationof 10 ppm, the compounds of Preparation Examples 6, 12 and 17 show weakactivity; the compounds of Preparation Examples 5 and 8 show goodactivity. At an exemplary active compound concentration of 100 ppm, forexample, the compounds of Preparation Examples 2 and 21 show weakactivity, and the compounds of Preparation Examples 6, 12 and 17 showgood activity.

Example M

Trichinella spiralis In-vitro

Test animals: Trichinella spiralis larvae Solvent: dimethyl suiphoxide

Trichinella spiralis larvae are isolated from skeletal muscles andsubcutaneous muscles of SPF/CFW1 mice and collected in aqueous 0.9% NaClcontaining 20 μg of sisomycin/ml. Per determination, 20 larvae areincubated in 2 ml of a nutrient solution (20 g of Bacto Casitone/l, 10 gof yeast extract/l, 5 g of glucose/l, 0.8 g of KH₂PO₄/l, 0.8 g ofK₂HPO₄; 10 g of sisomycin/ml and 1 μg of Canesten/ml; pH=7.2).

The incubation and the determination have been described in Martin etal., Pesticide Science (1996) 48, 343-349. 10 mg of the test compoundare dissolved in 0.5 ml of the stated solvent, and such an amount of theresulting solution is added to the incubation medium that the desiredconcentration is reached. The controls contain only the solvent.

After an incubation time of 5 days at a temperature of 19° C., theexperiment is terminated. The anthelmintic activity of a substance iscategorized into 4 stages. 0 means no activity, 1 means weak activity, 2means good activity and 3 means full activity (<50%, 50-75%, >75%, 100%of the larvae dead).

In this test, for example, at an exemplary active compound concentrationof 10 ppm, the compounds of Preparation Examples 5 and 8 show goodactivity. At an exemplary active compound concentration of 100 ppm, forexample, the compound of Preparation Example 6 shows good activity. Atan exemplary active compound concentration of 100 ppm, the compounds ofPreparation Examples 2, 10, 12, 17 and 21 show no activity in this test.

1. A compound of the formula (I)

in which X represents hydrogen, halogen, or alkyl, m represents aninteger from 3 to 10, n represents 0, 1, or 2, and Het represents agroup

 where R¹ represents hydrogen; mercapto; optionally halogen-substitutedalkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, or alkenyl;optionally substituted aryl; or optionally substituted heterocyclyl, Yrepresents oxygen or sulphur, and R² represents hydrogen; alkyl; oroptionally substituted aryl.
 2. A process for preparing a compound ofthe formula (I) according to claim 1 comprising (a) reacting a mercaptoderivative of the formula (II)Het-SH  (II)  in which Het is as defined for formula (I) of claim 1, ora salt thereof,  with a fluoroalkenyl halide of the formula (III)

in which X and m are each as defined for formula (I) of claim 1, and Halrepresents halogen,  in the presence of a diluent and optionally in thepresence of a basic reaction auxiliary, to form a heterocyclicfluoroalkenyl thioether of the formula (IA)

in which Het, X, and m are each as defined for formula (I) of claim 1,and (b) for preparing a compound of formula (I) in which n is 1 or 2,oxidizing the heterocyclic fluoroalkenyl thioether of the formula (IA)with an oxidizing agent, optionally in the presence of a diluent andoptionally in the presence of a catalyst.
 3. A compound of the formula(I) according to claim 1 in which X represents hydrogen, fluorine,chlorine, bromine, or C₁-C₄-alkyl, m represents an integer from 3 to 8,n represents 0 or 2, and Het represents a group

 where R¹ represents hydrogen; mercapto; C₁-C₈-alkyl, C₁-C₈-alkoxy,C₁-C₈-alkylthio, C₁-C₈-alkylsulphinyl, C₁-C₈-alkylsulphonyl, orC₂-C₈-alkenyl, each of which is optionally mono- or polysubstituted byidentical or different halogens; phenyl that is optionally mono- topentasubstituted by identical or different substituents selected fromthe group consisting of halogen, nitro, cyano, thiocyanato, andC₁-C₄-alkyl, C₁-C₄-alkoxy, or C₁-C₄-alkylthio, each of whichC₁-C₄-alkyl, C₁-C₄-alkoxy, or C₁-C₄-alkylthio is optionally mono- orpolysubstituted by identical or different halogens; or 5- or 6-memberedheterocyclyl having 1 to 3 N, O or S heteroatoms and that is optionallymono- to pentasubstituted by identical or different substituentsselected from the group consisting of halogen, nitro, cyano,thiocyanato, and C₁-C₄-alkyl, C₁-C₄-alkoxy, or C₁-C₄-alkylthio, each ofwhich C₁-C₄-alkyl, C₁-C₄-alkoxy, or C₁-C₄-alkylthio is optionally mono-or polysubstituted by identical or different halogens, Y representsoxygen or sulphur, and R² represents hydrogen or C₁-C₄-alkyl.
 4. Acompound of the formula (I) according to claim 1 in which X representshydrogen or fluorine, m represents integers from 3 to 6, n represents 0,and Het represents a group

 where R¹ represents hydrogen; sulphur; C₁-C₆-alkyl, C₁-C₆-alkoxy,C₁-C₆-alkylthio, C₁-C₆-alkylsulphinyl, C₁-C₆-alkylsulphonyl, orC₂-C₆-alkenyl, each of which is optionally mono- to pentasubstituted byidentical or different substituents selected from the group consistingof fluorine and chlorine; phenyl that is optionally mono- totrisubstituted by identical or different substituents selected from thegroup consisting of fluorine, chlorine, bromine, nitro, cyano,thiocyanato, and C₁-C₄-alkyl, C₁-C₄-alkoxy, or C₁-C₄-alkylthio, each ofwhich C₁-C₄-alkyl, C₁-C₄-alkoxy, or C₁-C₄-alkylthio is optionally mono-to pentasubstituted by identical or different substitutents selectedfrom the group consisting of fluorine and chlorine; or furyl, thienyl,pyrazolyl, pyridinyl, or pyrimidinyl, each of which is optionally mono-to trisubstituted by identical or different substituents selected fromthe group consisting of fluorine, chlorine, bromine, nitro, cyano,thiocyanato, and C₁-C₄-alkyl, C₁-C₄-alkoxy, or C₁-C₄-alkylthio, each ofwhich C₁-C₄-alkyl, C₁-C₄-alkoxy, or C₁-C₄-alkylthio is optionally mono-to pentasubstituted by identical or different substituents selected fromthe group consisting of fluorine and chlorine, Y represents oxygen orsulphur, and R² represents hydrogen or C₁-C₄-alkyl.
 5. A compound of theformula (I) according to claim 1 in which m represents 4, and Hetrepresents a group

 where R¹ represents hydrogen; mercapto; methyl, ethyl, n- or i-propyl,n-, i-, s-, or t-butyl, n-, i-, or neo-pentyl, methoxy, ethoxy, n- ori-propoxy, n-, i-, s-, or t-butoxy, methylthio, ethylthio, n- ori-propylthio, methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl,methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, each of whichis optionally mono- to pentasubstituted by identical or differentsubstituents selected from the group consisting of fluorine andchlorine; ethenyl, propenyl, butenyl, pentenyl, or hexenyl; ethenylthio,propenylthio, butenylthio, pentenylthio, or hexenylthio; ethylsulphinyl,propenylsulphinyl, butenylsulphinyl, pentenylsulphinyl, orhexenylsulphinyl; ethenylsulphonyl, propenylsulphonyl, butenylsulphonyl,pentenylsulphonyl, or hexenylsulphonyl; phenyl that is optionally mono-or disubstituted by identical or different substituents selected fromthe group consisting of fluorine, chlorine, nitro, cyano, thiocyanato,and methyl, ethyl, methoxy, ethoxy, methylthio, or ethylthio, each ofwhich methyl, ethyl, methoxy, ethoxy, methylthio, or ethylthio isoptionally mono- to pentasubstituted by identical or differentsubstituents selected from the group consisting of fluorine andchlorine; or thienyl or pyridinyl, each of which is optionally mono- ordisubstituted by identical or different substituents selected from thegroup consisting of fluorine, chlorine, nitro, cyano, thiocyanato, andmethyl, ethyl, methoxy, ethoxy, methylthio, or ethylthio, each of whichmethyl, ethyl, methoxy, ethoxy, methylthio, or ethylthio is optionallymono- to pentasubstituted by identical or different substituentsselected from the group consisting of fluorine and chlorine, Yrepresents oxygen or sulphur, and R² represents hydrogen, methyl, ethyl,or n- or i-propyl.
 6. A compound of the formula (I) according to claim 1in which Het represents the group

where R¹ and Y are each as defined for formula (I) of claim
 1. 7. Apesticide comprising a pesticidally effective amount of one or morecompounds of the formula (I) according to claim 1 and customaryextenders.
 8. A method for controlling pests comprising allowing one ormore compounds of the formula (I) according to claim 1 to act on pestsand/or their habitat.
 9. A method for controlling pests comprisingallowing a pesticide according to claim 7 to act on pests and/or theirhabitat.
 10. A process for preparing pesticides comprising mixing acompound of the formula (I) according to claim 1 with extenders and/orsurfactants.